CN104768894A - Interlayer for laminated glass, and laminated glass - Google Patents

Interlayer for laminated glass, and laminated glass Download PDF

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Publication number
CN104768894A
CN104768894A CN201380057044.1A CN201380057044A CN104768894A CN 104768894 A CN104768894 A CN 104768894A CN 201380057044 A CN201380057044 A CN 201380057044A CN 104768894 A CN104768894 A CN 104768894A
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China
Prior art keywords
mole
mentioned
vinyl
structural unit
layer
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Granted
Application number
CN201380057044.1A
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Chinese (zh)
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CN104768894B (en
Inventor
岛本伦男
岩本达矢
小松亮介
吉田章吾
丹野信幸
桥本崇男
小竹弘寿
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Denka Co Ltd
Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
Denki Kagaku Kogyo KK
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/001—Double glazing for vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/02—Windows; Windscreens; Accessories therefor arranged at the vehicle front, e.g. structure of the glazing, mounting of the glazing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31627—Next to aldehyde or ketone condensation product
    • Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)

Abstract

Provided are an interlayer for laminated glass and laminated glass using the interlayer for laminated glass. The interlayer for laminated glass enables the production of laminated glass exhibiting heightened sound insulating properties. The interlayer (1) for laminated glass according to the present invention includes a modified polyvinyl acetate and a plasticizing agent. The modified polyvinyl acetate contains a vinyl acetate structural unit and a fatty acid vinyl ester structural unit. The laminated glass according to the present invention is provided with a first laminated glass constituent member, a second laminated glass constituent member, and an interlayer sandwiched between the first and second laminated glass constituent members. The interlayer in the laminated glass according to the present invention is the interlayer for laminated glass described above.

Description

Intermediate film for laminated glasses and laminated glass
Technical field
The present invention relates to the intermediate film for laminated glasses used in the laminated glass of a kind of automobile and buildings etc.In addition, the present invention relates to a kind of laminated glass using this intermediate film for laminated glasses.
Background technology
Even if laminated glass is subject to external impact and damaged, the amount of dispersing of glass fragment is also few, excellent in safety.Therefore, above-mentioned laminated glass is widely used in automobile, rail truck, flyer, boats and ships and buildings etc.Above-mentioned laminated glass manufactures by being clamped into by intermediate coat between a pair sheet glass.
In recent years, in order to make laminated glass lighting, have studied the thickness of thinning laminated glass.But, if the thickness of thinning laminated glass, then sound-proofing step-down.When laminated glass low for sound-proofing is used for the windshield glass etc. of automobile, there is the problem that cannot obtain sound-proofing relative to the sound of about the 5000Hz range such as driving sound of wind noise or wiper fully.
Therefore, the sound-proofing improving laminated glass by changing intermediate coat material is studied.
As an example of intermediate film for laminated glasses, Patent Document 1 discloses following: a kind of pugging, it contains acetalizing degree is polyvinyl acetal resin 100 weight part of 60 ~ 85 % by mole, at least one metal-salt 0.001 ~ 1.0 weight part in an alkali metal salt and alkali earth metal salt and the softening agent more than 30 weight parts.This pugging using individual layer as intermediate coat, or can use as multilayer intermediate coat with other layer laminate.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-070200 publication
Summary of the invention
Invent problem to be solved
In the laminated glass using the intermediate coat recorded in above-mentioned patent documentation 1, although sound-proofing can be improved to a certain extent, require being further enhanced of sound-proofing.
In addition, in recent years, from using the fuel automobile of oil engine to evolve to the electromobile using electric motor and the hybrid vehicle etc. using oil engine and electric motor.Use the laminated glass special requirement used in the fuel automobile of oil engine compared with the sound-proofing under low frequency range.But, use the laminated glass used in the fuel automobile of oil engine to expect that the sound-proofing under high frequency region is high.To this, in the laminated glass used in the electromobile utilizing electric motor and hybrid vehicle, in order to effectively intercept the driving sound of electric motor, specially require the high sound-proofing at high frequency region.
When using the intermediate coat recorded in above-mentioned patent documentation 1 to form laminated glass, the sound-proofing of laminated glass to high frequency region is insufficient, therefore, the sound-proofing caused by coincidence effect sometimes cannot be avoided to reduce.Particularly this laminated glass sound-proofing under about 20 DEG C is insufficient sometimes.
At this, coincidence effect refers to following phenomenon: when sound wave is incident to sheet glass, due to rigidity and the inertia of sheet glass, shear wave is propagated in glass surface, and shear wave and incident sound resonate, its result cause sound through.
In addition, in recent years, in order to improve the sound-proofing of laminated glass, also studying excessive softening agent is added in intermediate coat.By adding excessive softening agent in intermediate coat, the sound-proofing of laminated glass can be improved.But when using excessive softening agent, softening agent oozes out on the surface of intermediate coat sometimes.
In addition, laminated glass, in outdoor application, therefore, is exposed to the condition of alkalescence sometimes.Existing intermediate coat be exposed to alkalescence condition time, sometimes intermediate coat can go bad, deterioration.Therefore, though preferred intermediate coat be exposed to alkalescence condition under, can prevent intermediate coat from going bad, deterioration performance (hereinafter also referred to as alkali resistance) also can be improved.
The object of the invention is to, provide a kind of and can improve the intermediate film for laminated glasses of the sound-proofing of the laminated glass obtained and use the laminated glass of this intermediate film for laminated glasses when for forming laminated glass.
Determinate object of the present invention is, provides a kind of laminated glass of obtaining of can improving when for forming laminated glass to the intermediate film for laminated glasses of the sound-proofing of high frequency region and the laminated glass using this intermediate film for laminated glasses.
Determinate object of the present invention is, provides a kind of and improves the intermediate film for laminated glasses of the alkali resistance of intermediate coat and use the laminated glass of this intermediate film for laminated glasses.
For the technical scheme of dealing with problems
According to wide in range aspect of the present invention, can provide a kind of intermediate film for laminated glasses, it contains modification polyvinyl acetate and softening agent, and described modification polyvinyl acetate has vinyl-acetic ester structural unit and vinyl fatty ester structural unit.
In certain particular aspects of intermediate film for laminated glasses of the present invention, in the described vinyl-acetic ester structural unit of described modification polyvinyl acetate and the total 100 % by mole of described vinyl fatty ester structural unit, preferably containing described vinyl-acetic ester structural unit more than 45 % by mole, containing described vinyl fatty ester structural unit less than 55 % by mole; More preferably containing described vinyl-acetic ester structural unit more than 50 % by mole, containing described vinyl fatty ester structural unit less than 50 % by mole.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described vinyl fatty ester structural unit is the structural unit being derived from vinyl fatty ester and importing, the carbonatoms of preferred described vinyl fatty ester is less than 20, and more preferably the carbonatoms of described vinyl fatty ester is more than 5 and less than 20.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described vinyl fatty ester is sad vinyl acetate, caprate, vinyl laurate, tetradecanoic acid ethene ester, vinyl palmitate, stearic acid vinyl ester, vinyl cinnamate or vinyl neodecanoate
Described vinyl fatty ester is sad vinyl acetate, caprate, vinyl laurate, tetradecanoic acid ethene ester, vinyl palmitate, stearic acid vinyl ester, vinyl cinnamate or vinyl neodecanoate.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described modification polyvinyl acetate has described vinyl-acetic ester structural unit, described vinyl fatty ester structural unit and is derived from the structural unit of the monomer with carboxyl.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described in there is carboxyl monomer be (methyl) vinylformic acid, toxilic acid, fumaric acid, β-crotonic acid, methylene-succinic acid, maleic mono-ester, fumaric monoalkylester or methylene-succinic acid monoesters.
In certain particular aspects of intermediate film for laminated glasses of the present invention, the described vinyl-acetic ester structural unit of described modification polyvinyl acetate, described vinyl fatty ester structural unit and be describedly derived from the total 100 % by mole of the structural unit of the monomer with carboxyl, containing described vinyl-acetic ester structural unit more than 45 % by mole and less than 98.99 % by mole, containing described vinyl fatty ester structural unit more than 1 % by mole and less than 50 % by mole, be derived from the structural unit more than 0.01 % by mole of the monomer with carboxyl described in containing and less than 5 % by mole.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described modification polyvinyl acetate, under the existence of compound with structural unit shown in following formula (X), makes described vinyl-acetic ester and described vinyl fatty ester generation copolymerization and obtains.
[chemical formula 1]
In described formula (X), X1 and X2 represents the alkyl of carbonatoms 1 ~ 12, hydrogen atom or metal-salt respectively, and Y1 represents carboxylic acid group, carboxylic acid ester groups, carboxylic metallic salt or hydrogen atom, and g represents the integer of 0 ~ 3, and h represents the integer of 0 ~ 12.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described modification polyvinyl acetate is under the existence of compound with structural unit shown in described formula (X), make described vinyl-acetic ester and described vinyl fatty ester generation copolymerization and obtain, in the total 100 % by mole of described vinyl-acetic ester and described vinyl fatty ester, described vinyl-acetic ester is more than 45 % by mole, and described vinyl fatty ester is less than 55 % by mole.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described modification polyvinyl acetate is under the existence of compound with structural unit shown in described formula (X), make described vinyl-acetic ester, described vinyl fatty ester and the described monomer with carboxyl carry out copolymerization and obtain, at described vinyl-acetic ester, described vinyl fatty ester and describedly have in the total 100 % by mole of the monomer of carboxyl, described vinyl-acetic ester is more than 45 % by mole and less than 98.99 % by mole, described vinyl fatty ester is more than 1 % by mole and less than 50 % by mole, the described monomer with carboxyl is more than 0.01 % by mole and less than 5 % by mole.
In certain particular aspects of intermediate film for laminated glasses of the present invention, the polymerization degree of described modification polyvinyl acetate is more than 1000 and less than 9000.
In certain particular aspects of intermediate film for laminated glasses of the present invention, this intermediate film for laminated glasses has the Rotating fields only possessing the first layer or the two-layer above rhythmo structure possessing the first layer and other layer, wherein, described the first layer contains described modification polyvinyl acetate and described softening agent.
In certain particular aspects of intermediate film for laminated glasses of the present invention, this intermediate film for laminated glasses possesses the first layer and is stacked on the second layer of first surface of described the first layer, and described the first layer contains described modification polyvinyl acetate and described softening agent.
In certain particular aspects of intermediate film for laminated glasses of the present invention, the described second layer contains polyvinyl acetal resin, and the degree of acetylation of polyvinyl acetal resin described in the described second layer is less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.
In certain particular aspects of intermediate film for laminated glasses of the present invention, this intermediate film for laminated glasses possesses third layer further, and it is stacked on the second surface contrary with described first surface of described the first layer.
In certain particular aspects of intermediate film for laminated glasses of the present invention, described third layer contains polyvinyl acetal resin, and the degree of acetylation of polyvinyl acetal resin described in described third layer is less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.
Laminated glass of the present invention possesses the first laminated glass component parts, the second laminated glass component parts and above-mentioned intermediate film for laminated glasses, and described intermediate film for laminated glasses is clipped between first, second laminated glass component parts described.
The effect of invention
Intermediate film for laminated glasses of the present invention contains modification polyvinyl acetate and softening agent, and, above-mentioned modification polyvinyl acetate has vinyl-acetic ester structural unit and vinyl fatty ester structural unit, therefore, the sound-proofing of the laminated glass using intermediate film for laminated glasses of the present invention can be improved.
Accompanying drawing explanation
Fig. 1 is the biopsy cavity marker devices sectional view of the intermediate film for laminated glasses schematically showing the first embodiment of the present invention.
Fig. 2 is the biopsy cavity marker devices sectional view of the intermediate film for laminated glasses schematically showing the second embodiment of the present invention.
Fig. 3 is for schematically showing the biopsy cavity marker devices sectional view of an example of the laminated glass using the intermediate film for laminated glasses shown in Fig. 1.
Fig. 4 is for schematically showing the biopsy cavity marker devices sectional view of an example of the laminated glass using the intermediate film for laminated glasses shown in Fig. 2.
Nomenclature
1 ... intermediate coat
1a ... first surface
1b ... second surface
2 ... the first layer
2a ... first surface
2b ... second surface
3 ... the second layer
3a ... the surface in outside
4 ... third layer
4a ... outer surface
11 ... laminated glass
16 ... laminated glass
21 ... first laminated glass component parts
22 ... second laminated glass component parts
31 ... intermediate coat
31a ... first surface
31b ... second surface
Embodiment
Below, details of the present invention is described.
Intermediate film for laminated glasses of the present invention contains modification polyvinyl acetate and softening agent.In intermediate film for laminated glasses of the present invention, above-mentioned modification polyvinyl acetate contains vinyl-acetic ester structural unit and vinyl fatty ester structural unit.
Intermediate film for laminated glasses of the present invention contains specific above-mentioned modification polyvinyl acetate and softening agent, therefore, can improve the sound-proofing of the laminated glass employing intermediate coat.Further, also can improve employ intermediate coat laminated glass to the sound-proofing of high frequency region.Particularly effectively can improve the sound-proofing of the high frequency region more than 3kHz.
Further, and be not compared with the existing polyvinyl acetate of above-mentioned modification polyvinyl acetate or the modifier of this polyvinyl acetate, the alkali resistance of above-mentioned modification polyvinyl acetate is high.Therefore, the alkali resistance of the intermediate coat containing above-mentioned modification polyvinyl acetate can be improved.If the alkali resistance of intermediate coat is high, even if the laminated glass then possessing this intermediate coat is in uses such as outdoors, intermediate coat is not perishable, not easily deterioration also.
Above-mentioned modification polyvinyl acetate, preferably under the existence of compound with the structural unit shown in following formula (X), makes described vinyl-acetic ester and described vinyl fatty ester generation copolymerization and obtains.Now, copolymerization can use the aftermentioned monomer with carboxyl as required further.
[chemical formula 2]
In described formula (X), X1 and X2 represents the alkyl of carbonatoms 1 ~ 12, hydrogen atom or metal-salt respectively, and Y1 represents carboxylic acid group, carboxylic acid ester groups, carboxylic metallic salt or hydrogen atom, and g represents the integer of 0 ~ 3, and h represents the integer of 0 ~ 12.
Be not compared with the existing polyvinyl acetate of modification polyvinyl acetate or the modifier of this polyvinyl acetate, under the existence of compound with structural unit shown in formula (X), make vinyl-acetic ester and vinyl fatty ester generation copolymerization and the CV value of the modification polyvinyl acetate obtained is little, and the modification polyvinyl acetate obtained is the particle of narrow particle distribution.Therefore, the homogeneity of the intermediate coat obtained by using above-mentioned modification polyvinyl acetate can be improved.Character not easily according to intermediate coat local difference and different, in multiple intermediate coat, character not easily produces inequality.
In addition, if above-mentioned intermediate coat in region at least partially containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent.With regard to above-mentioned intermediate coat, sound-proofing and the alkali resistance in the region containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent can be improved.
Intermediate film for laminated glasses of the present invention also can have the Rotating fields only possessing the first layer or the two-layer above rhythmo structure possessing the first layer and other layer.Now, above-mentioned the first layer contains above-mentioned modification polyvinyl acetate and above-mentioned softening agent.
Below, with reference to accompanying drawing while be described concrete embodiment of the present invention and embodiment, clear and definite the present invention thus.
Fig. 1 schematically shows the intermediate film for laminated glasses of the first embodiment of the present invention with biopsy cavity marker devices sectional view.
Intermediate coat 1 shown in Fig. 1 is for having the intermediate film for laminated glasses of three layer stacked structure.Intermediate coat 1 possesses: the first layer 2, be stacked on the second layer 3 of the first surface 2a side of the first layer 2 and be stacked on the third layer 4 of second surface 2b side of the first layer 2.
In addition, between the first layer 2 and the second layer 3 and between the first layer 2 and third layer 4, also can distinguish other layer of lamination.As other layer, can enumerate: the layer containing thermoplastic resins such as polyvinyl acetal resins and the layer containing polyethylene terephthalate etc.
Intermediate coat 1 is containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent.In intermediate coat 1, the first layer 2 is preferably containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent.When the first layer 2 is containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent, the second layer 3 and third layer 4 can not contain above-mentioned modification polyvinyl acetate and above-mentioned softening agent respectively, also can contain above-mentioned modification polyvinyl acetate and above-mentioned softening agent.
The first layer 2 is middle layer.When the first layer 2 is containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent, the first layer 2 works mainly as pugging.The second layer 3, third layer 4 are protective layer, are upper layer in the present embodiment.The first layer 2 is added between the second layer 3, third layer 4.Therefore, intermediate coat 1 has the multilayered structure in order second layer 3, the first layer 2, third layer 4 being carried out to lamination.
The second layer 3 can be identical with the composition of third layer 4, also can be different.If at second, third layer 3, containing polyvinyl acetal resin in 4, then the second layer 3, bonding force between third layer 4 and laminated glass component parts fully uprise.Further, the resistance to penetrability employing the laminated glass of intermediate coat further uprises, and the operability of intermediate coat also uprises.
Intermediate coat also can be only at the first surface 2a side lamination second layer 3 of the first layer 2, and not at the intermediate coat of the second surface 2b side lamination third layer 4 of the first layer 2.
Fig. 2 schematically shows the intermediate film for laminated glasses of the second embodiment of the present invention with biopsy cavity marker devices sectional view.
Intermediate coat 31 shown in Fig. 2 is the intermediate film for laminated glasses of the structure only with the first layer.Intermediate coat 31 is containing above-mentioned modification polyvinyl acetate and above-mentioned softening agent.
Below, the details of each composition contained in the details of the details of each composition contained in the details of intermediate film for laminated glasses of the present invention, this intermediate coat, the first layer forming intermediate film for laminated glasses of the present invention, the second layer, third layer and this first layer, the second layer, third layer is described.
(thermoplastic resin)
Above-mentioned intermediate film for laminated glasses contains modification polyvinyl acetate.Above-mentioned the first layer is preferably containing modification polyvinyl acetate.Above-mentioned modification polyvinyl acetate is thermoplastic resin.Above-mentioned modification polyvinyl acetate can be used singly or in combination of two or more.
Above-mentioned modification polyvinyl acetate contains vinyl-acetic ester structural unit and vinyl fatty ester structural unit.Above-mentioned vinyl-acetic ester structural unit is be derived from the structural unit that vinyl-acetic ester imports.Above-mentioned vinyl fatty ester structural unit is be derived from the structural unit that vinyl fatty ester imports.Above-mentioned vinyl fatty ester is different from vinyl-acetic ester.Above-mentioned modification polyvinyl acetate obtains by making the polymerization of the Polymerizable composition containing vinyl-acetic ester and vinyl fatty ester.
In the above-mentioned vinyl-acetic ester structural unit of preferred above-mentioned modification polyvinyl acetate and the total 100 % by mole of above-mentioned vinyl fatty ester structural unit, containing vinyl-acetic ester structural unit more than 10 % by mole, containing vinyl fatty ester structural unit less than 90 % by mole.From the viewpoint of obtaining the further excellent modification polyvinyl acetate of alkali resistance, above-mentioned modification polyvinyl acetate is preferably in the total 100 % by mole of above-mentioned vinyl-acetic ester structural unit and above-mentioned vinyl fatty ester structural unit, containing vinyl-acetic ester structural unit more than 45 % by mole, containing vinyl fatty ester structural unit less than 55 % by mole; More preferably containing vinyl-acetic ester structural unit more than 50 % by mole, containing vinyl fatty ester structural unit less than 50 % by mole; Further preferably containing vinyl-acetic ester structural unit more than 70 % by mole, containing vinyl fatty ester structural unit less than 30 % by mole; Further preferably containing vinyl-acetic ester structural unit more than 75 % by mole, containing vinyl fatty ester structural unit less than 25 % by mole.In addition, if the ratio of above-mentioned vinyl fatty ester structural unit is below the above-mentioned upper limit, then the cementability of intermediate coat and intensity further uprise.
Above-mentioned modification polyvinyl acetate is particularly preferably in the total 100 % by mole of above-mentioned vinyl-acetic ester structural unit and above-mentioned vinyl fatty ester structural unit, containing vinyl-acetic ester structural unit less than 99.9 % by mole, containing vinyl fatty ester structural unit more than 0.1 % by mole; More preferably containing vinyl-acetic ester structural unit less than 99 % by mole, containing vinyl fatty ester structural unit more than 1 % by mole; Further preferably containing vinyl-acetic ester structural unit less than 95 % by mole, containing vinyl fatty ester structural unit more than 5 % by mole; Further preferably containing vinyl-acetic ester structural unit less than 90 % by mole, containing vinyl fatty ester structural unit more than 10 % by mole.If the ratio of above-mentioned vinyl fatty ester structural unit is more than above-mentioned lower limit, then the alkali resistance of modification polyvinyl acetate further uprises.
Above-mentioned modification polyvinyl acetate, preferably under the existence of compound (following, be sometimes designated as compounds X) with the structural unit shown in above-mentioned formula (X), makes above-mentioned vinyl-acetic ester and above-mentioned vinyl fatty ester copolymerization and obtains.
The multipolymer that beyond vinyl-acetic ester and vinyl fatty ester and vinyl-acetic ester and beyond vinyl fatty ester polymerizable compound (copolymer composition) is formed is comprised in above-mentioned modification polyvinyl acetate (1).Above-mentioned modification polyvinyl acetate be beyond vinyl-acetic ester and vinyl fatty ester and vinyl-acetic ester and beyond vinyl fatty ester polymerizable compound formed multipolymer time, in overall texture unit 100 % by mole, the ratio of vinyl-acetic ester structural unit is preferably more than 50 % by mole, be more preferably more than 60 % by mole, more preferably more than 70 % by mole, be particularly preferably more than 80 % by mole, most preferably be more than 90 % by mole.As beyond vinyl-acetic ester and polymerizable compound beyond vinyl fatty ester, can enumerate: there is the monomer of carboxyl, (methyl) acrylic compound and distyryl compound, isoprenoid etc.
Beyond vinyl-acetic ester and vinyl fatty ester and vinyl-acetic ester and beyond vinyl fatty ester polymerizable compound (copolymer composition) preferably has the monomer of carboxyl.Above-mentioned modification polyvinyl acetate can have the structural unit being derived from the monomer with carboxyl, also can not have.The above-mentioned structural unit being derived from the monomer with carboxyl is be derived from the structural unit that the monomer with carboxyl imports.By importing the structural unit being derived from the monomer with carboxyl, sound-proofing and the alkali resistance of intermediate coat uprise effectively, and the cementability of intermediate coat further uprises.Particularly when intermediate coat have the second layer described later, three layers, have by above-mentioned modification polyvinyl acetate the structural unit being derived from the monomer with carboxyl, the first layer further uprises relative to the second layer, the bonding force of three layers.
From the sound-proofing and the alkali resistance that effectively improve intermediate coat, and the viewpoint further improving the cementability of intermediate coat is considered, the above-mentioned monomer with carboxyl is preferably (methyl) vinylformic acid, toxilic acid, fumaric acid, β-crotonic acid, methylene-succinic acid, maleic mono-ester, fumaric monoalkylester or methylene-succinic acid monoesters.
From the sound-proofing and the alkali resistance that effectively improve intermediate coat, and the viewpoint further improving the cementability of intermediate coat is considered, above-mentioned modification polyvinyl acetate is preferably at above-mentioned vinyl-acetic ester structural unit, above-mentioned vinyl fatty ester structural unit and be above-mentionedly derived from the total 100 % by mole of the structural unit of the monomer with carboxyl, be more than 45 % by mole and less than 98.99 % by mole containing above-mentioned vinyl-acetic ester structural unit, be more than 1 % by mole and less than 50 % by mole containing above-mentioned vinyl fatty ester structural unit, be more than 0.01 % by mole and less than 5 % by mole containing the above-mentioned structural unit being derived from the monomer with carboxyl.
When manufacture has the modification polyvinyl acetate of vinyl-acetic ester structural unit and vinyl fatty ester structural unit, by under the existence of above-claimed cpd X, make vinyl-acetic ester and vinyl fatty ester generation copolymerization, the little and particle of narrow diameter distribution of CV value can be obtained.In addition, in this copolyreaction, the residual quantity of unreacted monomer tails off.Tailed off by the residual quantity of unreacted monomer, the alkali resistance of above-mentioned modification polyvinyl acetate also can uprise.Therefore, above-mentioned modification polyvinyl acetate, preferably under the existence of above-claimed cpd X, makes vinyl-acetic ester and vinyl fatty ester generation copolymerization and obtains.
Under the existence of above-claimed cpd X, when making vinyl-acetic ester and vinyl fatty ester generation copolymerization, preferably use suspension polymerization.The further excellent modification polyvinyl acetate of alkali resistance can be obtained by suspension polymerization.
Above-mentioned modification polyvinyl acetate is preferably under the existence of above-claimed cpd X, make vinyl-acetic ester and vinyl fatty ester generation copolymerization and obtain, in the total 100 % by mole of above-mentioned vinyl-acetic ester and above-mentioned vinyl fatty ester, containing vinyl-acetic ester more than 10 % by mole, containing vinyl fatty ester less than 90 % by mole.From the viewpoint of obtaining the further excellent modification polyvinyl acetate of alkali resistance, above-mentioned modification polyvinyl acetate is preferably under the existence of above-claimed cpd X, in the total 100 % by mole of above-mentioned vinyl-acetic ester and above-mentioned vinyl fatty ester, make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of more than 45 % by mole and less than 55 % by mole and obtain; More preferably make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of more than 50 % by mole and less than 50 % by mole and obtain; Further make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of more than 70 % by mole and less than 30 % by mole and obtain; Preferably make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of more than 75 % by mole and less than 25 % by mole further and obtain.In addition, if the usage quantity of above-mentioned vinyl fatty ester is below the above-mentioned upper limit, then the cementability of intermediate coat and intensity further uprise.
Above-mentioned modification polyvinyl acetate is preferably under the existence of above-claimed cpd X, in the total 100 % by mole of above-mentioned vinyl-acetic ester and above-mentioned vinyl fatty ester, make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of less than 99.9 % by mole and more than 0.1 % by mole and obtain; More preferably make the vinyl fatty ester generation copolymerization of more than the nytril of less than 99 % by mole % by mole and obtain; Further make the vinyl fatty ester generation copolymerization of the vinyl-acetic ester of less than 95 % by mole and more than 5 % by mole and obtain; Preferably make the vinyl fatty ester generation copolymerization of the nytril more than 0 % by mole of less than 90 % by mole further and obtain.If the usage quantity of above-mentioned vinyl fatty ester is more than above-mentioned lower limit, then the alkali resistance of modification polyvinyl acetate further uprises.
Above-mentioned modification polyvinyl acetate is preferably under the existence of above-claimed cpd X, above-mentioned vinyl-acetic ester, above-mentioned vinyl fatty ester and the above-mentioned monomer with carboxyl is made to carry out copolymerization and obtain, at above-mentioned vinyl-acetic ester, above-mentioned vinyl fatty ester with above-mentionedly have in the total 100 % by mole of the monomer of carboxyl, above-mentioned vinyl-acetic ester is more than 45 % by mole and less than 98.99 % by mole, above-mentioned vinyl fatty ester is more than 1 % by mole and less than 50 % by mole, and the above-mentioned monomer with carboxyl is more than 0.01 % by mole and less than 5 % by mole.If the usage quantity of above-mentioned vinyl fatty ester is below the above-mentioned upper limit, then the cementability of intermediate coat and intensity further uprise.If the usage quantity above-mentioned with the monomer of carboxyl is below the above-mentioned upper limit, then the sound-proofing of intermediate coat and alkali resistance uprise effectively, and the cementability of intermediate coat further uprises.
Under the existence of above-claimed cpd X, when making vinyl-acetic ester and vinyl fatty ester generation copolymerization, preferably use polymerizing catalyst, preferably use polymerization regulator, preferably use the dispersion medium containing water.As above-mentioned polymerizing catalyst and above-mentioned polymerization regulator, existing known polymerizing catalyst and polymerization regulator can be used.
Above-claimed cpd X is such as by obtaining making the multipolymer of vinyl-acetic ester and alkyl maleates generation copolymerization carry out saponification.Above-claimed cpd X obtains preferably by making the multipolymer of vinyl-acetic ester and alkyl maleates generation copolymerization carry out saponification.As above-mentioned alkyl maleates, can enumerate: dimethyl maleate and ethyl maleate.As above-mentioned alkyl maleates, preferred dimethyl maleate and ethyl maleate.
The number-average molecular weight of above-claimed cpd X is preferably more than 3800, is preferably less than 28500.Above-mentioned number-average molecular weight be by gel permeation chromatography obtain in the flat molecular weight of the number of standard polyoxyethylene glycol.If the number-average molecular weight of above-claimed cpd X is below more than above-mentioned lower limit and the above-mentioned upper limit; then under the existence of above-claimed cpd X; in the aqueous dispersion medium containing above-claimed cpd X, vinyl-acetic ester, vinyl fatty ester and water; when making vinyl-acetic ester and vinyl fatty ester generation copolymerization, the balance between the solvability of above-claimed cpd X in water and the protective colloid of vinyl-acetic ester and vinyl fatty ester becomes good.In above-mentioned aqueous dispersion medium 100 % by weight, the content of above-claimed cpd X is preferably more than 0.05 % by weight, is preferably less than 0.5 % by weight.If the content of above-claimed cpd X is below more than above-mentioned lower limit and the above-mentioned upper limit, then further can maintain protective colloid well, the viscosity of aqueous dispersion medium further becomes appropriateness, and (being total to) polyreaction is further carried out effectively.
From the viewpoint of obtaining the further excellent modification polyvinyl acetate of alkali resistance, the carbonatoms of above-mentioned vinyl fatty ester is preferably less than 30, is more preferably less than 20, and more preferably less than 18, be particularly preferably less than 16, most preferably be less than 14.If the carbonatoms of above-mentioned vinyl fatty ester is less than 20, then can obtain the very high and particle of the modification polyvinyl acetate that CV value root is little further of alkali resistance.In addition, if carbonatoms is below the above-mentioned upper limit, then the cementability of intermediate coat and intensity further uprise.
From the viewpoint of obtaining the further excellent modification polyvinyl acetate of alkali resistance, the carbonatoms of above-mentioned vinyl fatty ester is preferably more than 1, is more preferably more than 5, and more preferably more than 8, be particularly preferably more than 10, most preferably be more than 12.If the carbonatoms of above-mentioned vinyl fatty ester is more than 5, then alkali resistance becomes very high.In addition, if above-mentioned carbonatoms is more than above-mentioned lower limit, then the water tolerance of intermediate coat further uprises.
As above-mentioned vinyl fatty ester, can enumerate: sad vinyl acetate, caprate, vinyl laurate, tetradecanoic acid ethene ester, vinyl palmitate, stearic acid vinyl ester, vinyl cinnamate or vinyl neodecanoate and mountain Yu's vinyl acetate.Also the vinyl fatty ester beyond them can be used.Above-mentioned vinyl fatty ester can be used alone a kind, also can combinationally use two or more.
From the viewpoint of obtaining the further excellent modification polyvinyl acetate of alkali resistance, as above-mentioned vinyl fatty ester, be preferably sad vinyl acetate, caprate, vinyl laurate, tetradecanoic acid ethene ester, vinyl palmitate, stearic acid vinyl ester, vinyl cinnamate or vinyl neodecanoate.
The polymerization degree of above-mentioned modification polyvinyl acetate is preferably more than 1000, is more preferably less than 9000, is more preferably less than 7000, and more preferably less than 5000.If the polymerization degree of above-mentioned modification polyvinyl acetate is below more than above-mentioned lower limit and the above-mentioned upper limit, then, when obtaining intermediate coat and laminated glass, melt viscosity becomes appropriateness, and the productivity of intermediate coat further uprises.From the viewpoint of increasing productivity further, the polymerization degree of above-mentioned modification polyvinyl acetate is more preferably more than 1500, is more preferably less than 4000.
In addition, the polymerization degree of above-mentioned modification polyvinyl acetate is obtained by the method according to JIS K6725 " polyvinyl acetate test method ".
From the viewpoint of making the alkali resistance of modification polyvinyl acetate further good, the above-mentioned modification polyvinyl acetate before cooperation is preferably median particle diameter and is more than 100 μm and the particle of less than 800 μm.Preferred use median particle diameter is that the particle below more than above-mentioned lower limit and the above-mentioned upper limit obtains intermediate coat or the first layer as modification polyvinyl acetate.Preferred use median particle diameter is the particle of the modification polyvinyl acetate below more than above-mentioned lower limit and the above-mentioned upper limit, and coordinates this modification polyvinyl acetate and softening agent and obtain above-mentioned intermediate coat or above-mentioned the first layer.
From the viewpoint of the intermediate coat obtaining homogeneous, the CV value of the particle of the above-mentioned modification polyvinyl acetate before cooperation is preferably less than 0.8%, is more preferably less than 0.5%.Preferred use above-mentioned CV value obtains intermediate coat or the first layer as modification polyvinyl acetate for the particle below the above-mentioned upper limit.The above-mentioned CV of preferred use be for the above-mentioned upper limit below the particle of modification polyvinyl acetate, and coordinate this modification polyvinyl acetate and softening agent and obtain above-mentioned intermediate coat or above-mentioned the first layer.Above-mentioned CV value through type: the standard deviation/volume average particle size (D50) × 100 of size-grade distribution and obtaining.
Above-mentioned intermediate coat is preferably containing polyvinyl acetal resin (following, to be sometimes designated as polyvinyl acetal resin (0)).Above-mentioned the first layer is preferably containing polyvinyl acetal resin (following, to be sometimes designated as polyvinyl acetal resin (1)).If above-mentioned intermediate coat contains polyvinyl acetal resin (0), if particularly above-mentioned the first layer contains polyvinyl acetal resin (1), then the production efficiency of intermediate film for laminated glasses uprises.Above-mentioned polyvinyl acetal resin (0) and above-mentioned polyvinyl acetal resin (1) respectively preferred degree of acetylation are (following lower than the polyvinyl acetal resin of 8 % by mole; also referred to as " polyvinyl acetal resin (A) "); or degree of acetylation is the polyvinyl acetal resin (hereinafter also referred to as " polyvinyl acetal resin (B) ") of more than 8 % by mole.
The degree of acetylation (a) of above-mentioned polyvinyl acetal resin (A) is lower than 8 % by mole; be preferably less than 7.5 % by mole, be preferably less than 7 % by mole, be preferably less than 6 % by mole; be preferably less than 5 % by mole; be preferably more than 0.1 % by mole, be preferably more than 0.5 % by mole, be preferably more than 0.8 % by mole; be preferably more than 1 % by mole; be preferably more than 2 % by mole, be preferably more than 3 % by mole, be preferably more than 4 % by mole.If above-mentioned degree of acetylation (a) is for below the above-mentioned upper limit and more than above-mentioned lower limit, then the consistency of polyvinyl acetal resin (A) and softening agent further uprises, and further can improve the sound-proofing of laminated glass.
The preferred lower limit of the acetalizing degree (a) of above-mentioned polyvinyl acetal resin (A) is 68 % by mole, preferred lower limit is 70 % by mole, preferred lower limit is 71 % by mole further, being particularly preferably lower limit is 72 % by mole, the preferred upper limit is 85 % by mole, the preferred upper limit is 83 % by mole, and the preferred upper limit is 81 % by mole further, and the particularly preferred upper limit is 79 % by mole.If above-mentioned acetalizing degree (a) is for more than above-mentioned lower limit, then further can improve the sound-proofing of laminated glass.If above-mentioned acetalizing degree (a) is for below the above-mentioned upper limit, then can shorten for the manufacture of the reaction times required for polyvinyl acetal resin (A).
Hydroxyl containing ratio (a) of above-mentioned polyvinyl acetal resin (A) is preferably less than 30 % by mole, be preferably less than 27.5 % by mole, be preferably less than 27 % by mole, be preferably less than 26 % by mole, be preferably less than 25 % by mole, be preferably less than 24 % by mole, be preferably less than 23 % by mole, be preferably less than 16 % by mole, be preferably more than 18 % by mole, be preferably more than 19 % by mole, be preferably more than 20 % by mole.If above-mentioned hydroxyl containing ratio (a) is for below the above-mentioned upper limit, then further can improve the sound-proofing of laminated glass.If above-mentioned hydroxyl containing ratio (a) is for more than above-mentioned lower limit, then further can improve the bonding force of intermediate coat.
Above-mentioned polyvinyl acetal resin (A) is preferably polyvinyl butyral resin.
The degree of acetylation (b) of above-mentioned polyvinyl acetal resin (B) is more than 8 % by mole; be preferably more than 9 % by mole; be preferably more than 10 % by mole, be preferably more than 11 % by mole, be preferably more than 12 % by mole; be preferably less than 30 % by mole; be preferably less than 28 % by mole, be preferably less than 26 % by mole, be preferably less than 24 % by mole; be preferably less than 20 % by mole, be preferably less than 19.5 % by mole.If above-mentioned degree of acetylation (b) is for more than above-mentioned lower limit, then further can improve the sound-proofing of laminated glass.If above-mentioned degree of acetylation (b) is for below the above-mentioned upper limit, then can shorten for the manufacture of the reaction times required for polyvinyl acetal resin (B).Wherein, from the viewpoint of what further shorten for the manufacture of the reaction times required for polyvinyl acetal resin (B), the degree of acetylation (b) of above-mentioned polyvinyl acetal resin (B) is preferably lower than 20 % by mole.
The preferred lower limit of the acetalizing degree (b) of above-mentioned polyvinyl acetal resin (B) is 50 % by mole, preferred lower limit is 52.5 % by mole, preferred lower limit is 54 % by mole further, being particularly preferably lower limit is 60 % by mole, the preferred upper limit is 80 % by mole, the preferred upper limit is 77 % by mole, and the preferred upper limit is 74 % by mole further, and the particularly preferred upper limit is 71 % by mole.If above-mentioned acetalizing degree (b) is for more than above-mentioned lower limit, then further can improve the sound-proofing of laminated glass.If above-mentioned acetalizing degree (b) is for below the above-mentioned upper limit, then can shorten for the manufacture of the reaction times required for polyvinyl acetal resin (B).
Hydroxyl containing ratio (b) of above-mentioned polyvinyl acetal resin (B) is preferably less than 30 % by mole, be preferably less than 27.5 % by mole, be preferably less than 27 % by mole, be preferably less than 26 % by mole, be preferably more than 25 % by mole, be preferably more than 18 % by mole, be preferably more than 20 % by mole, be preferably more than 22 % by mole, be preferably more than 23 % by mole.If the containing ratio (b) of above-mentioned hydroxyl is for below the above-mentioned upper limit, then further can improve the sound-proofing of laminated glass.If above-mentioned hydroxyl containing ratio (b) is for more than above-mentioned lower limit, then further can improve the bonding force of intermediate coat.
Above-mentioned polyvinyl acetal resin (B) is preferably polyvinyl butyral resin.
Above-mentioned polyvinyl acetal resin (A) and above-mentioned polyvinyl acetal resin (B) preferably utilize aldehyde carry out acetalation to the polyvinyl alcohol resin of mean polymerisation degree more than 3000 and obtain.Above-mentioned aldehyde is preferably the aldehyde of carbonatoms 1 ~ 10, is more preferably the aldehyde of carbonatoms 4 or 5.The preferred lower limit of the mean polymerisation degree of above-mentioned polyvinyl alcohol resin is 3010, preferred lower limit is 3050, preferred lower limit is 3500, and preferred lower limit is 3600, and preferred lower limit is 4000, preferred lower limit is 4050, the preferred upper limit is 7000, and the preferred upper limit is 6000, and the preferred upper limit is 5000, the preferred upper limit is 4900, and the preferred upper limit is 4500.In above-mentioned the first layer, above-mentioned polyvinyl acetal resin (A), above-mentioned polyvinyl acetal resin (B) particularly preferably carry out acetalation to mean polymerisation degree more than 3000 and lower than the polyvinyl alcohol resin of 4000 and obtain.Particularly from further suppressing, fully improve the sound-proofing of laminated glass to the growth of the generation of foaming laminated glass and foaming and easily can form the aspect consideration of intermediate coat, for obtaining polyvinyl acetal resin (A) in above-mentioned the first layer, the mean polymerisation degree of above-mentioned polyvinyl alcohol resin of polyvinyl acetal resin (B) is preferably more than 3010, be more preferably more than 3020, be preferably less than 4000, more preferably less than 4000, more preferably less than 3800, be particularly preferably less than 3600, most preferably be less than 3500.
When above-mentioned intermediate coat contains modification polyvinyl acetate and polyvinyl acetal resin (0), in the total 100 % by weight of modification polyvinyl acetate and polyvinyl acetal resin (0), ratio shared by modification polyvinyl acetate is preferably more than 1 % by weight, be more preferably more than 10 % by weight, more preferably more than 20 % by weight, be particularly preferably more than 50 % by weight, be preferably less than 99 % by weight, be more preferably less than 90 % by weight, more preferably less than 80 % by weight.If aforementioned proportion is below the above-mentioned upper limit, then the production efficiency of intermediate film for laminated glasses further uprises.If aforementioned proportion is more than above-mentioned lower limit, then further can improve the sound-proofing of laminated glass.When above-mentioned intermediate coat only possesses above-mentioned the first layer, the ratio of above-mentioned modification polyvinyl acetate is preferably more than above-mentioned lower limit and below the above-mentioned upper limit.
When above-mentioned the first layer contains modification polyvinyl acetate and polyvinyl acetal resin (1), in the total 100 % by weight of modification polyvinyl acetate and polyvinyl acetal resin (1), ratio shared by modification polyvinyl acetate is preferably more than 1 % by weight, be more preferably more than 10 % by weight, more preferably more than 20 % by weight, be particularly preferably more than 50 % by weight, be preferably less than 99 % by weight, be more preferably less than 90 % by weight, more preferably less than 80 % by weight.If aforementioned proportion is below the above-mentioned upper limit, then the production efficiency of intermediate film for laminated glasses further uprises.If aforementioned proportion is more than above-mentioned lower limit, then further can improve the sound-proofing of laminated glass.
The above-mentioned second layer, preferably containing thermoplastic resin, more preferably contains polyvinyl acetal resin (following, to be sometimes designated as polyvinyl acetal resin (2)).Above-mentioned third layer, preferably containing thermoplastic resin, more preferably contains polyvinyl acetal resin (following, to be sometimes designated as polyvinyl acetal resin (3)).If the second layer, third layer contain polyvinyl acetal resin (2), polyvinyl acetal resin (3), then the second layer, bonding force between third layer and laminated glass component parts fully uprise.Above-mentioned two layers, in third layer, above-mentioned thermoplastic resin can be used alone a kind respectively, also can combinationally use two or more.Above-mentioned polyvinyl acetal resin (2), above-mentioned polyvinyl acetal resin (3) can be used alone a kind respectively, also can combinationally use two or more.The thermoplastic resin used in the above-mentioned second layer, third layer is not particularly limited.The polyvinyl acetal (2) used in the above-mentioned second layer, third layer, polyvinyl acetal (3) are not particularly limited.
As above-mentioned thermoplastic resin, can enumerate: polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, urethane resin and polyvinyl alcohol resin etc.
The degree of acetylation of above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) is preferably more than 0 % by mole respectively; be more preferably more than 0.1 % by mole; more preferably more than 0.5 % by mole; be preferably less than 30 % by mole; be more preferably less than 20 % by mole, be further preferably less than 15 % by mole, more preferably less than 10 % by mole; be particularly preferably less than 5 % by mole, most preferably be less than 3 % by mole.If above-mentioned degree of acetylation is below the above-mentioned upper limit, the resistance to penetrability of intermediate coat and laminated glass uprises.Further, if degree of acetylation is below the above-mentioned upper limit, then oozing out of softening agent can be suppressed.
In addition, if the degree of acetylation of the polyvinyl acetal resin in above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) is less than 3 % by mole, then the mechanical properties of intermediate coat further improves.This result, the resistance to penetrability of laminated glass further uprises.
Above-mentioned degree of acetylation is the value representing mole fraction with percentage (% by mole), and the value that described mole fraction obtains by deducting the ethene base unit weight of acetal radical institute bonding and the ethene base unit weight of hydroxyl institute bonding from total ethene base unit weight of main chain is tried to achieve divided by total ethene base unit weight of main chain.The ethene base unit weight of above-mentioned acetal radical institute bonding can measure according to such as JIS K6728 " polyvinyl butyral acetal test method ".
Above-mentioned polyvinyl acetal resin (A) and above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) such as manufacture by utilizing aldehyde to carry out acetalation to polyvinyl alcohol.Above-mentioned polyvinyl alcohol such as obtains by carrying out saponification to polyvinyl acetate.
For obtaining above-mentioned polyvinyl acetal resin (2), the average polymer of above-mentioned polyvinyl alcohol of polyvinyl acetal resin (3) is preferably more than 200, be more preferably more than 500, more preferably more than 1600, be particularly preferably more than 2600, most preferably be more than 2700, be preferably less than 5000, be more preferably less than 4000, more preferably less than 3500.If above-mentioned average polymer is more than above-mentioned lower limit, then the resistance to penetrability of laminated glass further uprises.If above-mentioned mean polymerisation degree is below the above-mentioned upper limit, then the shaping of intermediate coat becomes easy.
In addition, the mean polymerisation degree of above-mentioned polyvinyl alcohol is obtained by the method according to JIS K6726 " polyvinyl alcohol test method ".
The carbonatoms of acetal radical contained in above-mentioned polyvinyl acetal resin is not particularly limited.The aldehyde used when manufacturing above-mentioned polyvinyl acetal resin is not particularly limited.The carbonatoms of the acetal radical in above-mentioned polyvinyl acetal resin is preferably 3 ~ 5, from the viewpoint of boosting productivity, is more preferably 3 or 4.
Above-mentioned aldehyde is not particularly limited.As above-mentioned aldehyde, usually can preferably use carbonatoms be 1 ~ 10 aldehyde.Be the aldehyde of 1 ~ 10 as above-mentioned carbonatoms, such as, can enumerate: propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, valeraldehyde, 2-ethyl butyraldehyde, n-hexyl aldehyde, n-octaldehyde, n-nonyl aldehyde, n-capric aldehyde, formaldehyde, acetaldehyde and phenyl aldehyde etc.Wherein, preferred propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, n-hexyl aldehyde or valeraldehyde, more preferably propionic aldehyde, butyraldehyde-n or isobutyric aldehyde, further preferred butyraldehyde-n.Above-mentioned aldehyde can be used singly or in combination of two or more.
Above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) are preferably polyvinyl butyral resin respectively.Intermediate film for laminated glasses of the present invention preferably contains polyvinyl butyral resin respectively as above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) contained in the above-mentioned second layer, third layer.The synthesis of polyvinyl butyral resin is easy.Further, by using polyvinyl butyral resin, the bonding force of intermediate coat relative to laminated glass component parts is further moderately shown.Further, photostabilization and weathering resistance etc. further uprise.
In above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3), hydroxy radical content rate (amount of hydroxyl groups) is preferably more than 20 % by mole respectively, be more preferably more than 25 % by mole, more preferably more than 30 % by mole, be preferably less than 50 % by mole, be more preferably less than 45 % by mole, more preferably less than 40 % by mole, be particularly preferably less than 35 % by mole.If the containing ratio of above-mentioned hydroxyl is more than above-mentioned lower limit, then the resistance to penetrability of laminated glass further uprises.In addition, if the containing ratio of above-mentioned hydroxyl is below the above-mentioned upper limit, then not easily produce oozing out of softening agent.Further, the flexibility of intermediate coat uprises, and the operation of intermediate coat becomes easy.
In above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3), the containing ratio of hydroxyl is the value representing mole fraction with percentage (% by mole), and described mole fraction is tried to achieve divided by total ethene base unit weight of main chain by the ethene base unit weight of hydroxyl institute bonding.The ethene base unit weight of above-mentioned hydroxyl institute bonding is such as by carrying out mensuration to obtain according to JISK6726 " polyvinyl alcohol test method ".
The acetalizing degree (being butyraldehyde degree when polyvinyl butyral acetal) of above-mentioned polyvinyl acetal resin (2), polyvinyl acetal resin (3) is preferably more than 55 % by mole respectively, be more preferably more than 60 % by mole, more preferably more than 63 % by mole, be preferably less than 85 % by mole, be more preferably less than 75 % by mole, more preferably less than 70 % by mole.If above-mentioned acetalizing degree is more than above-mentioned lower limit, then polyvinyl acetal resin (2), polyvinyl acetal resin (3) uprise with the consistency of softening agent.If above-mentioned acetalizing degree is below the above-mentioned upper limit, then shorten for the manufacture of the reaction times required for polyvinyl acetal resin.
Above-mentioned acetalizing degree is the value representing mole fraction with percentage (% by mole), and described mole fraction is tried to achieve divided by total ethene base unit weight of main chain by the ethene base unit weight of acetal radical institute bonding.
Above-mentioned acetalizing degree measures by utilizing the containing ratio of method to degree of acetylation and hydroxyl according to JIS K6728 " polyvinyl butyral acetal test method "; mole fraction is calculated by the measurement result obtained; then, the containing ratio deducting degree of acetylation and hydroxyl from 100 % by mole calculates.
In addition; when polyvinyl acetal resin is polyvinyl butyral resin, above-mentioned acetalizing degree (butyral degree) and degree of acetylation can carry out measuring according to the method for JIS K6728 " polyvinyl butyral acetal test method " or ASTM D1396-92 the result that obtains by utilizing and calculate.Measure preferably by the method according to ASTM D1396-92.
From the viewpoint of the sound-proofing further improving laminated glass, in the above-mentioned second layer, the degree of acetylation of above-mentioned polyvinyl acetal resin is preferably less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.From the viewpoint of the sound-proofing further improving laminated glass, the degree of acetylation of the above-mentioned polyvinyl acetal resin in above-mentioned third layer is preferably less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.
(softening agent)
Above-mentioned intermediate coat contains softening agent (following, to be sometimes designated as softening agent (0)).Above-mentioned the first layer is preferably containing softening agent (following, to be sometimes designated as softening agent (1)).The above-mentioned second layer is preferably containing softening agent (following, to be sometimes designated as softening agent (2)).Above-mentioned third layer is preferably containing softening agent (following, to be sometimes designated as softening agent (3)).Above-mentioned softening agent (0), softening agent (1), softening agent (2), softening agent (3) can be used alone a kind respectively, also can combinationally use two or more.In addition, when above-mentioned intermediate coat only possesses above-mentioned the first layer, above-mentioned softening agent (0) is identical with above-mentioned softening agent (1).
As above-mentioned softening agent (0), softening agent (1), softening agent (2), softening agent (3), such as, can enumerate: the organic ester softening agent such as unitary organic acid acetic and poly-basic organic acid ester and the organic phosphoric acid such as organic phosphoric acid softening agent and organic phosphorous acid softening agent softening agent etc.Wherein, preferred organic ester plasticizer.Above-mentioned softening agent (0), softening agent (1), softening agent (2), softening agent (3) are preferably aqueous softening agent.
As above-mentioned unitary organic acid acetic, be not particularly limited, such as, can enumerate: undertaken reacting by glycol and unitary organic acid and ester etc. that the diol ester that obtains and triethylene glycol or tripropylene glycol and unitary organic acid are formed.As above-mentioned glycol, can enumerate: triethylene glycol, TEG and tripropylene glycol etc.As above-mentioned unitary organic acid, can enumerate: butyric acid, isopropylformic acid, caproic acid, 2 Ethylbutanoic acid, enanthic acid, n-caprylic acid, 2 ethyl hexanoic acid, pelargonic acid and capric acid etc.
As above-mentioned poly-basic organic acid ester, be not particularly limited, such as, can enumerate: the ester cpds that poly-basic organic acid is formed with the alcohol of the straight or branched structure with carbonatoms 4 ~ 8.As above-mentioned poly-basic organic acid, can enumerate: hexanodioic acid, sebacic acid and nonane diacid etc.
As above-mentioned organic ester softening agent, be not particularly limited, can enumerate: triethylene glycol two-2 Ethylbutanoic acid ester, triethylene glycol two-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol two-n-caprylic acid ester, triethylene glycol two-positive heptanoate, TEG two-positive heptanoate, Uniflex DBS, dioctyl azelate, dibutyl carbitol adipic acid ester, ethylene glycol bisthioglycolate-2 Ethylbutanoic acid ester, 1,3-PD two-2 Ethylbutanoic acid ester, Isosorbide-5-Nitrae-propylene glycol two-2 Ethylbutanoic acid ester, Diethylene Glycol two-2 Ethylbutanoic acid ester, Diethylene Glycol two-2-ethylhexanoate, dipropylene glycol two-2 Ethylbutanoic acid ester, triethylene glycol two-2-ethylpentanoic ester, TEG two-2 Ethylbutanoic acid ester, Diethylene Glycol dicaprylate, Polycizer W 260, dihexyl adipate, hexanodioic acid dibutyl ester, hexanodioic acid hexyl cyclohexyl, the mixture of hexanodioic acid heptyl ester and hexanodioic acid ester in the ninth of the ten Heavenly Stems, diisononyl adipate, diisodecyl adipate, hexanodioic acid heptyl ester in the ninth of the ten Heavenly Stems, Uniflex DBS, oil modification sebacic acid alkyd, and the mixture etc. of phosphoric acid ester and adipic acid ester.Also the organic ester softening agent beyond them can be used.
As above-mentioned organic phosphoric acid softening agent, be not particularly limited, such as, can enumerate: three butoxy ethyl ester of phosphoric acid, isodecyl phenylester and tricresyl phosphate isopropyl ester etc.
From the viewpoint of the sound-proofing further improving laminated glass, in intermediate coat, in softening agent (0) and the first layer, softening agent (1) is preferably two ester plasticizers shown in following formula (1) respectively.From the viewpoint of the sound-proofing further improving laminated glass, in the second layer, third layer, softening agent (2), (3) are preferably two ester plasticizers shown in following formula (1) respectively.
[chemical formula 3]
In above-mentioned formula (1), R1 and R2 represents the organic group of carbonatoms 5 ~ 10 respectively, and R3 represents ethylidene, isopropylidene or positive propylidene, and p represents the integer of 3 ~ 10.
Above-mentioned softening agent (0), softening agent (1) are preferably containing at least a kind in adipic acid ester, triethylene glycol two-2-ethylhexanoate (3GO) and triethylene glycol two-2 Ethylbutanoic acid ester (3GH), more preferably containing at least a kind in triethylene glycol two-2-ethylhexanoate and triethylene glycol two-2 Ethylbutanoic acid ester, further preferably containing triethylene glycol two-2-ethylhexanoate.
Above-mentioned softening agent (2), softening agent (3) preferably containing at least a kind in triethylene glycol two-2-ethylhexanoate (3GO) and triethylene glycol two-2 Ethylbutanoic acid ester (3GH), more preferably contain triethylene glycol two-2-ethylhexanoate respectively.
In above-mentioned intermediate coat, relative to above-mentioned modification polyvinyl acetate 100 weight part, the content of above-mentioned softening agent (0) is preferably more than 25 weight parts, is preferably below 80 weight parts.From the viewpoint of the sound-proofing further improving laminated glass, in above-mentioned intermediate coat, relative to above-mentioned modification polyvinyl acetate 100 weight part, the content of above-mentioned softening agent (0) is more preferably more than 30 weight parts, be more preferably below 70 weight parts, more preferably below 60 weight parts, be particularly preferably below 50 weight parts.If the content of above-mentioned softening agent (0) is more than above-mentioned lower limit, then the flexibility of intermediate coat uprises, and the operation of intermediate coat becomes easy, and the resistance to penetrability of laminated glass further uprises.If the content of above-mentioned softening agent (0) is below the above-mentioned upper limit, then the transparency of intermediate coat further uprises.When above-mentioned intermediate coat only possesses above-mentioned the first layer, the content of above-mentioned softening agent (0) is preferably more than above-mentioned lower limit and below the above-mentioned upper limit.
In above-mentioned intermediate coat, relative to total 100 weight part of thermoplastic resin 100 weight part or above-mentioned modification polyvinyl acetate and polyvinyl acetal resin, the content of above-mentioned softening agent (0) is preferably more than 25 weight parts, is preferably below 80 weight parts.From the viewpoint of the sound-proofing further improving laminated glass, in above-mentioned intermediate coat, relative to total 100 weight part of thermoplastic resin 100 weight part or above-mentioned modification polyvinyl acetate and polyvinyl acetal resin, the content of above-mentioned softening agent (0) is more preferably more than 30 weight parts, be more preferably below 70 weight parts, more preferably below 60 weight parts, be particularly preferably below 50 weight parts.If the content of above-mentioned softening agent (0) is more than above-mentioned lower limit, then the flexibility of intermediate coat uprises, and the operation of intermediate coat becomes easy, and the resistance to penetrability of laminated glass further uprises.If the content of above-mentioned softening agent (0) is below the above-mentioned upper limit, then the transparency of intermediate coat further uprises.When above-mentioned intermediate coat only possesses above-mentioned the first layer, the content of above-mentioned softening agent (0) is preferably more than above-mentioned lower limit and below the above-mentioned upper limit.
In above-mentioned the first layer, relative to above-mentioned modification polyvinyl acetate 100 weight part, the content of above-mentioned softening agent (1) is preferably more than 25 weight parts, is preferably below 80 weight parts.From the viewpoint of the sound-proofing further improving laminated glass, in above-mentioned the first layer, relative to above-mentioned modification polyvinyl acetate 100 weight part, the content of above-mentioned softening agent (1) is more preferably more than 30 weight parts, be more preferably below 70 weight parts, more preferably below 60 weight parts, be particularly preferably below 50 weight parts.In above-mentioned the first layer, relative to total 100 weight part of above-mentioned modification polyvinyl acetate and above-mentioned polyvinyl acetal resin (1), the content of above-mentioned softening agent (1) is preferably more than 25 weight parts, is preferably below 80 weight parts.From the viewpoint of the sound-proofing further improving laminated glass, in above-mentioned the first layer, relative to total 100 weight part of above-mentioned modification polyvinyl acetate and above-mentioned polyvinyl acetal resin (1), the content of above-mentioned softening agent (1) is more preferably more than 30 weight parts, be more preferably below 70 weight parts, more preferably below 60 weight parts, be particularly preferably below 50 weight parts.In addition, if the content of above-mentioned softening agent (1) is more than above-mentioned lower limit, then the flexibility of intermediate coat uprises, and the operation of intermediate coat becomes easy, and the resistance to penetrability of laminated glass further uprises.If the content of above-mentioned softening agent (1) is below the above-mentioned upper limit, then the transparency of intermediate coat further uprises.
In the above-mentioned second layer, relative to above-mentioned polyvinyl acetal resin (2) 100 weight part, the content of above-mentioned softening agent (2) is preferably more than 5 weight parts, be more preferably more than 10 weight parts, more preferably more than 15 weight parts, be preferably below 50 weight parts, be more preferably below 45 weight parts, more preferably below 40 weight parts.In above-mentioned third layer, relative to above-mentioned polyvinyl acetal resin (3) 100 weight part, the content of above-mentioned softening agent (3) is preferably more than 5 weight parts, be more preferably more than 10 weight parts, more preferably more than 15 weight parts, be preferably below 50 weight parts, be more preferably below 45 weight parts, more preferably below 40 weight parts.If the content of above-mentioned softening agent (2), softening agent (3) is more than above-mentioned lower limit, then the flexibility of intermediate coat uprises, and the operation of intermediate coat becomes easy.If the content of above-mentioned softening agent (2), softening agent (3) is below the above-mentioned upper limit, then the resistance to penetrability of laminated glass further uprises.
Relative to polyvinyl acetal resin (2) 100 weight part above-mentioned in the above-mentioned second layer, in the above-mentioned second layer, the content of above-mentioned softening agent (2) is (following, sometimes content (2) is designated as) preferably few relative to the content (following, to be sometimes designated as content (1)) of above-mentioned modification polyvinyl acetate 100 weight part in above-mentioned the first layer than softening agent (1) above-mentioned in above-mentioned the first layer.In addition, relative to polyvinyl acetal resin (3) 100 weight part above-mentioned in above-mentioned third layer, in above-mentioned third layer, the content (following, to be sometimes designated as content (3)) of above-mentioned softening agent (3) is preferably few relative to the content (1) of modification polyvinyl acetate 100 weight part above-mentioned in above-mentioned the first layer than softening agent (1) above-mentioned in above-mentioned the first layer.Above-mentioned content (2) is preferably few than above-mentioned content (1).In addition, above-mentioned content (3) is preferably few than above-mentioned content (1).Fewer than above-mentioned content (1) by above-mentioned content (2), content (3), the resistance to penetrability of laminated glass further uprises.
Above-mentioned content (1) is preferably more than 1 weight part respectively with the absolute value of the absolute value of the difference of above-mentioned content (2) and the difference of above-mentioned content (1) and above-mentioned content (3), be more preferably more than 2 weight parts, more preferably more than 10 weight parts, be particularly preferably more than 15 weight parts, most preferably be more than 20 weight parts, be preferably below 40 weight parts, be more preferably below 35 weight parts, more preferably below 30 weight parts.If above-mentioned content (1) is more than above-mentioned lower limit with the absolute value of the difference of above-mentioned content (2), content (3), then the sound-proofing of laminated glass further uprises, if below the above-mentioned upper limit, then the resistance to penetrability of laminated glass further uprises.
(other composition)
Above-mentioned intermediate coat, above-mentioned the first layer, the above-mentioned second layer and above-mentioned third layer can contain the additives such as UV light absorber, antioxidant, photostabilizer, fire retardant, static inhibitor, pigment, dyestuff, bonding force conditioning agent, resistance to humectant, white dyes and infrared absorbent respectively as required.These additives can be used singly or in combination of two or more.
(intermediate film for laminated glasses)
From the viewpoint of the sound-proofing further improving laminated glass, the peak temperature of the Tan δ occurred in lowest temperature side that intermediate film for laminated glasses of the present invention records under frequency 1Hz is preferably less than 0 DEG C.
Sound-proofing under the low temperature further improving laminated glass, the maximum value of the Tan δ in the peak temperature of the Tan δ occurred in lowest temperature side recorded under frequency 1Hz is preferably more than 1.15, is more preferably more than 1.25.
Sound-proofing under the high temperature further improving laminated glass, the maximum value of the Tan δ in the peak temperature of the Tan δ occurred in highest temperature side recorded under frequency 1Hz is preferably more than 0.50.
It should be noted that, when measuring the maximum value of the above-mentioned peak temperature of the Tan δ occurred in lowest temperature side, the maximum value of the Tan δ in the peak temperature of the Tan δ of lowest temperature side appearance and the Tan δ in the peak temperature of the Tan δ of highest temperature side appearance, preferably intermediate film for laminated glasses keeping under the environment of 23 DEG C was measured after 1 month.
The thickness of above-mentioned the first layer is preferably more than 0.02mm, is more preferably more than 0.05mm, is preferably below 1.8mm, is more preferably below 0.5mm.If the thickness of above-mentioned the first layer is that below more than above-mentioned lower limit and the above-mentioned upper limit, then the thickness of intermediate coat can not become blocked up, and the sound-proofing of laminated glass further uprises.
The thickness of the above-mentioned second layer, third layer is preferably more than 0.1mm respectively, is more preferably more than 0.2mm, is preferably below 1mm, is more preferably below 0.5mm.If the thickness of the above-mentioned second layer, third layer is that below more than above-mentioned lower limit and the above-mentioned upper limit, then the thickness of intermediate coat can not become blocked up, and the sound-proofing of laminated glass further uprises, and, oozing out of softening agent can be suppressed.
The thickness of intermediate film for laminated glasses of the present invention is preferably more than 0.1mm, is more preferably more than 0.25mm, is preferably below 3mm, is more preferably below 1.5mm.If the thickness of intermediate coat is more than above-mentioned lower limit, then the resistance to penetrability of laminated glass fully uprises.If the thickness of intermediate coat is below the above-mentioned upper limit, then the transparency of intermediate coat further becomes good.
The manufacture method of intermediate film for laminated glasses of the present invention is not particularly limited.As the manufacture method of this intermediate coat, existing known method can be used.Such as can enumerate: the manufacture method etc. of modification polyvinyl acetate or polyvinyl acetal resin, softening agent and other composition of coordinating as required being carried out to the mixing intermediate coat that is shaped.Produce to be suitable for continuous print, the manufacture method of preferred extrusion molding.
Above-mentioned compounding process is not particularly limited.As the method, such as, can enumerate: the method using forcing machine, plastometer, kneader, Ben Baili Banbury mixer or stack etc.Wherein, producing to be suitable for continuous print, preferably using the method for forcing machine, more preferably using the method for biaxial extruder.It should be noted that, intermediate film for laminated glasses of the present invention can after making the first layer and the second layer, third layer respectively, the first layer and the second layer, third layer are carried out to lamination and obtain multilayer intermediate coat, also out can carry out lamination to the first layer and the second layer, third layer and obtain intermediate coat by co-extrusion.
From the viewpoint of the manufacture efficiency excellence of intermediate coat, preferably in the above-mentioned second layer, third layer, contain identical polyvinyl acetal resin, more preferably in the above-mentioned second layer, third layer, contain identical polyvinyl acetal resin and identical softening agent, the further preferred above-mentioned second layer, third layer are formed by identical resin combination.
(laminated glass)
Fig. 3 represents the intermediate film for laminated glasses of an embodiment of the invention with sectional view.
Laminated glass 11 shown in Fig. 3 possesses intermediate coat 1 and the first laminated glass component parts 21, second laminated glass component parts 22.Intermediate coat 1 sandwiches between the first laminated glass component parts 21, second laminated glass component parts 22.The first laminated glass component parts 21 is had at the first surface 1a superimposed layer of intermediate coat 1.The second laminated glass component parts 22 is had at the second surface 1b superimposed layer contrary with the first surface 1a of intermediate coat 1.The first laminated glass component parts 21 is had at the outer surface 3a superimposed layer of the second layer 3.The second laminated glass component parts 22 is had at the outer surface 4a superimposed layer of third layer 4.
Laminated glass 16 shown in Fig. 4 possesses intermediate coat 31 and the first laminated glass component parts 21, second laminated glass component parts 22.Intermediate coat 31 sandwiches between the first laminated glass component parts 21, second laminated glass component parts 22.The first laminated glass component parts 21 is had at the first surface 31a superimposed layer of intermediate coat 31.The second laminated glass component parts 22 is had at the second surface 31b superimposed layer contrary with the first surface 31a of intermediate coat 31.
As mentioned above, laminated glass of the present invention possess the first laminated glass component parts, the second laminated glass component parts and be added to this first laminated glass form, between the second laminated glass component parts intermediate coat, as this intermediate coat, intermediate film for laminated glasses of the present invention can be used.
As above-mentioned first laminated glass component parts, the second laminated glass component parts, can enumerate: sheet glass and PET (polyethylene terephthalate) film etc.The laminated glass sandwiching intermediate coat between 2 sheet glass is not only by above-mentioned laminated glass, and be also included within the laminated glass sandwiching intermediate coat between sheet glass and PET film etc.Laminated glass is the multilayer body possessing sheet glass, preferably uses at least 1 sheet glass.
As above-mentioned sheet glass, can enumerate: unorganic glass and synthetic glass.As above-mentioned unorganic glass, can enumerate: float flat glass, hot line absorb sheet glass, hot line reflector plate glass, polishing sheet glass, embossing plate glass, wired sheet glass, clamp sheet glass and green glass etc.Above-mentioned synthetic glass is the synthetic resins glass that alternative unorganic glass uses.As above-mentioned synthetic glass, polycarbonate plate and poly-(methyl) acrylic resin board etc. can be enumerated.As above-mentioned poly-(methyl) acrylic resin board, poly-(methyl) methyl acrylate plate etc. can be enumerated.
The thickness of above-mentioned first laminated glass component parts, the second laminated glass component parts is not particularly limited, preferably in the scope of 1 ~ 5mm.When above-mentioned laminated glass component parts is sheet glass, the thickness of this sheet glass is preferably in the scope of 1 ~ 5mm.When above-mentioned laminated glass component parts is PET film, the thickness of this PET film is preferably in the scope of 0.03 ~ 0.5mm.
The manufacture method of above-mentioned laminated glass is not particularly limited.Such as between above-mentioned first laminated glass component parts, the second laminated glass component parts, clamp above-mentioned intermediate coat, by extrusion roll or put into rubber pad carry out reducing pressure suction or to remaining in the first laminated glass component parts, air between the second laminated glass component parts and intermediate coat carries out degassed.Then, at about 70 ~ 110 DEG C, carry out pre-glued and obtain multilayer body.Then, multilayer body put into autoclave or it is suppressed, crimping under the pressure of about 120 ~ 150 DEG C and 1 ~ 1.5MPa.As above laminated glass can be obtained.
Laminated glass can be used for automobile, rail truck, flyer, boats and ships and buildings etc.Laminated glass also may be used for the purposes beyond these purposes.Above-mentioned intermediate coat is preferably intermediate coat for building or for motor vehicle, is more preferably for motor vehicle intermediate coat.Above-mentioned laminated glass is preferably laminated glass for building or for motor vehicle, is more preferably for motor vehicle laminated glass.Above-mentioned intermediate coat and above-mentioned laminated glass also can be used for the purposes beyond these purposes.Above-mentioned intermediate coat and above-mentioned laminated glass can be preferred for using the electromobile of electric motor and using the hybrid-electric car of oil engine and electric motor.Laminated glass can be used for windshield glass, the side glass, below glass or roof glass etc. of automobile.
Below, enumerate embodiment to be described in further detail the present invention.The present invention is not limited to these embodiments.
(synthesis example 1)
(1) synthesis of the compound of compounds X is equivalent to
Vinyl-acetic ester 17 weight part, methyl alcohol 14 weight part, dimethyl maleate 0.023 weight part, methylene-succinic acid 0.257 weight part and Diisopropyl azodicarboxylate 0.17 weight part are put into aggregation container.After carrying out nitrogen displacement in above-mentioned aggregation container, to being heated to boiling in aggregation container.
In addition, the mixed solution that vinyl-acetic ester 6 weight part, methyl alcohol 5 weight part and dimethyl maleate 0.207 weight part are mixed is prepared.In above-mentioned aggregation container, add above-mentioned mixed solution continuously carry out being polymerized until percent polymerization reaches 75%, the moment reaching 90% at percent polymerization stops polymerization.Then, remove unpolymerized vinyl-acetic ester by ordinary method, obtain polymkeric substance.Use sodium hydroxide and utilize ordinary method to carry out saponification to the polymkeric substance obtained.Then, at 90 DEG C, carry out 90 minutes warm air dryings, obtain the compound being equivalent to compounds X that several molecular-weight average 11000 and saponification deg are 88.0 % by mole.
The absorbancy of the aqueous solution under wavelength 270nm containing the compound 0.2 % by weight being equivalent to compounds X obtained and water 99.8 % by weight is 1.0.In addition, the aqueous solution of sample solution concentration 0.2w/v% is used to utilize GPC to measure at 40 DEG C the number-average molecular weight being equivalent to the compound of compounds X obtained.
(2) synthesis of modification polyvinyl acetate
Prepare the glass aggregation container possessing reflux exchanger, dropping funnel, temperature take into account nitrogen introducing port.Compound 0.1 weight part being equivalent to compounds X putting into ion exchanged water 270 weight part in this aggregation container and obtain, carries out heating and stirring, makes the compound dissolution being equivalent to compounds X.
Then, the temperature in above-mentioned aggregation container is made to be 58 DEG C, add and make it carry out polymerization 6 hours as lauroyl peroxide 0.08 weight part of polymerization starter, vinyl acetate monomer 100 weight part and vinyl neodecanoate 20 weight part, obtain the particle of modification polyvinyl acetate.
(synthesis example 2 ~ 8)
When carrying out suspension polymerization when obtaining modification polyvinyl acetate, the usage quantity of the kind of compound used, vinyl-acetic ester, the kind (carbonatoms) of vinyl fatty ester, the usage quantity of vinyl fatty ester and the polymerization degree of modification polyvinyl acetate that obtains are set shown in table 1 described as follows respectively like that, in addition, modification polyvinyl acetate is obtained in the same manner as synthesis example 1.
(synthesis example 9)
(1) synthesis of the compound of compounds X is equivalent to
Vinyl-acetic ester 17 weight part, methyl alcohol 14 weight part, dimethyl maleate 0.023 weight part, methylene-succinic acid 0.257 weight part and Diisopropyl azodicarboxylate 0.17 weight part are put into aggregation container.After carrying out nitrogen displacement in above-mentioned aggregation container, boiling will be heated in aggregation container.
In addition, the mixed solution that vinyl-acetic ester 6 weight part, methyl alcohol 5 weight part and dimethyl maleate 0.207 weight part are mixed is prepared.In above-mentioned aggregation container, add above-mentioned mixed solution continuously carry out being polymerized until percent polymerization reaches 75%, the moment reaching 90% at percent polymerization stops polymerization.Then, remove unpolymerized vinyl-acetic ester by ordinary method, obtain polymkeric substance.Use sodium hydroxide and utilize ordinary method to carry out saponification to the polymkeric substance obtained.Then, at 90 DEG C, carry out 90 minutes warm air dryings, obtain the compound being equivalent to compounds X that several molecular-weight average 11000 and saponification deg are 88.0 % by mole.
The absorbancy of the aqueous solution under wavelength 270nm containing the compound 0.2 % by weight being equivalent to compounds X obtained and water 99.8 % by weight is 1.0.In addition, the aqueous solution of sample solution concentration 0.2w/v% is used to utilize GPC to measure at 40 DEG C the number-average molecular weight being equivalent to the compound of compounds X obtained.
(2) synthesis of modification polyvinyl acetate
Prepare the glass aggregation container possessing reflux exchanger, dropping funnel, temperature take into account nitrogen introducing port.Compound 0.1 weight part being equivalent to compounds X putting into ion exchanged water 270 weight part in this aggregation container and obtain, carries out heating and stirring, makes the compound dissolution being equivalent to compounds X.
Then, the temperature in above-mentioned aggregation container is made to be 58 DEG C, add and make it be polymerized 6 hours as lauroyl peroxide 0.08 weight part of polymerization starter, vinyl acetate monomer 100 weight part, vinyl neodecanoate 20 weight part and single-ethylhexyl maleate 0.3 weight part, obtain the particle of modification polyvinyl acetate.
(synthesis example 10 ~ 15)
When obtaining modification polyvinyl acetate, the usage quantity of the usage quantity of the kind of the compound of use, vinyl-acetic ester, the kind with the monomer of carboxyl and the monomer with carboxyl is set shown in table 2 described as follows respectively like that, in addition, modification polyvinyl acetate is obtained in the same manner as synthesis example 9.
(evaluation of modification polyvinyl acetate)
(1) polymerization degree of modification polyvinyl acetate
Measure according to JIS K6725 " polyvinyl acetate test method " polymerization degree to the modification polyvinyl acetate obtained.
(2) residual vinyl acetate amount of monomer (unreacted monomer amount)
Based food additive official compendium the 7th edition " vinyl acetate resin " purity test measures remaining vinyl acetate monomer amount (unreacted monomer amount).
(3) median particle diameter of modification polyvinyl acetate
Use laser diffraction formula particle size distribution device (Shimadzu Corporation manufactures " SALD-2000 ") and in mensuration pond, add the size-grade distribution of distilled water to the modification polyvinyl acetate obtained and measure, obtain median particle diameter.
(4) homogeneity of the particle diameter of modification polyvinyl acetate
Use laser diffraction formula particle size distribution device (Shimadzu Corporation manufactures " SALD-2000 ") and in mensuration pond, add the size-grade distribution of distilled water to the modification polyvinyl acetate obtained and measure.CV value (standard deviation/volume average particle size (D50) × 100 of size-grade distribution) is utilized to judge the homogeneity of the particle diameter of modification polyvinyl acetate.CV value is less, and particle diameter is more even.Following benchmark is utilized to judge the homogeneity of the particle diameter of modification polyvinyl acetate
[determinating reference of the homogeneity of modification polyvinyl acetate particle diameter]
Zero: CV value is less than 0.5%
△: CV value is more than 0.5% and be less than 0.8%
×: CV value is more than 0.8%
(5) alkali resistance of modification polyvinyl acetate
The modification polyvinyl acetate 3g obtained is dissolved in acetone 97g, flows on fluororesin film.Under room temperature 23 ± 2 DEG C, humidity 50 ± 5%RH environment, make lysate on fluororesin film dry 3 days, obtain the film (thickness 100 μm) of modification polyvinyl acetate.The film of the modification polyvinyl acetate obtained is flooded 24 hours in 70 DEG C in 5 % by weight aqueous sodium hydroxide solutions.Following benchmark is utilized to judge the alkali resistance of modification polyvinyl acetate
[determinating reference of modification polyvinyl acetate alkali resistance]
00: before and after dipping, film does not change
Zero: the surface of dipping caudacoria a little gonorrhoea occurs
△: see film generation albefaction after dipping
×: there is the exception beyond albefaction in dipping caudacoria
The details of the modification polyvinyl acetate obtained and evaluation result are shown in following table 1,2.In addition, in following table 1,2, (2) unreacted monomer amount be the situation of " less than 150 " compared with the situation of " less than 300 ", unreacted monomer is few.In following table 1, the usage quantity (% by mole) of the usage quantity (% by mole) of vinyl-acetic ester and vinyl fatty ester represents the usage quantity in the total 100 % by mole being used for vinyl-acetic ester when (be total to) is polymerized and vinyl fatty ester.The ratio (% by mole) of vinyl-acetic ester structural unit and the ratio (% by mole) of vinyl fatty ester structural unit refer to: in the modification polyvinyl acetate obtained vinyl-acetic ester structural unit and vinyl fatty ester structural unit total 100 % by mole in ratio.In following table 2, the usage quantity (mole) of the usage quantity (% by mole) of vinyl-acetic ester, the usage quantity (% by mole) of vinyl fatty ester and the monomer with carboxyl refers to: vinyl-acetic ester when being polymerized for (being total to), vinyl fatty ester and have carboxyl monomer total 100 % by mole in usage quantity.The ratio (% by mole) of vinyl-acetic ester structural unit, the ratio (% by mole) of vinyl fatty ester structural unit and the structural unit (% by mole) being derived from the monomer with carboxyl refer to: the vinyl-acetic ester structural unit in the modification polyvinyl acetate obtained, vinyl fatty ester structural unit and be derived from the monomer with carboxyl structural unit total 100 % by mole in ratio.
In embodiment and comparative example, use polyvinyl butyral resin (a), polyvinyl butyral resin (b).The containing ratio of the butyral degree (acetalizing degree) of polyvinyl butyral resin (a), polyvinyl butyral resin (b), degree of acetylation and hydroxyl measures according to the method for ASTMD1396-92.In addition, when being measured by JIS K6728 " polyvinyl butyral acetal test method ", the numerical value that also display is same with the method according to ASTM D1396-92.
Polyvinyl butyral resin (a) (PVB (a)): containing ratio 23.7 % by mole, the acetalation of degree of acetylation 12.8 % by mole, butyral degree 63.5 % by mole, hydroxyl use butyraldehyde-n
Polyvinyl butyral resin (b) (PVB (b)): containing ratio 30.5 % by mole, the acetalation of degree of acetylation 1 % by mole, butyral degree 68.5 % by mole, hydroxyl use butyraldehyde-n
(embodiment 1)
Utilize mixing roll mixing fully using modification polyvinyl acetate 100 weight part obtained in synthesis example 1 with as triethylene glycol two-2-ethylhexanoate (3GO) 60 weight part of softening agent, obtain middle layer composition.
To polyvinyl butyral resin (b) 100 weight part with carry out mixing fully as triethylene glycol two-2-ethylhexanoate (3GO) 35 weight part of softening agent, obtain protective layer used composition.
Use coextrusion machine to form the middle layer composition obtained and protective layer used composition, make the intermediate coat (thickness 0.8mm) with protective layer B (thickness 0.35mm)/middle layer A (thickness 0.1mm)/protective layer B (thickness 0.35mm) rhythmo structure.
The multilayer intermediate coat obtained is cut out vertical 30mm × horizontal 320mm., between 2 transparent float glasses (vertical 25mm × horizontal 305mm × thickness 2.0mm), add multilayer intermediate coat, keep 30 minutes at 90 DEG C by vacuum laminator, carry out vacuum pressing, obtain multilayer body.In multilayer body, the middle membrane portion exposed is cut, obtain laminated glass from glass.
(embodiment 2 ~ 8)
By being used for the kind of the modification polyvinyl acetate of middle layer A and setting like that as described in Table 3 for the protection of the content of the softening agent of layer B, in addition, obtain intermediate coat and laminated glass similarly to Example 1.
(comparative example 1)
By being used for the contamination of the polyvinyl butyral resin of middle layer A and protective layer B, the contamination of softening agent sets as described in Table 3 like that, in addition, obtains intermediate coat and laminated glass similarly to Example 1.
(embodiment 9)
To modification polyvinyl acetate 100 weight part obtained in synthesis example 9 with to utilize mixing roll to carry out as triethylene glycol two-2-ethylhexanoate (3GO) 40 weight part of softening agent mixing fully, obtain middle layer composition.
To polyvinyl butyral resin (b) 100 weight part with carry out mixing fully as triethylene glycol two-2-ethylhexanoate (3GO) 37.5 weight part of softening agent, obtain protective layer used composition.
Use coextrusion machine to form the middle layer composition obtained and protective layer used composition, make the multilayer intermediate coat (thickness 0.8mm) with protective layer B (thickness 0.35mm)/middle layer A (thickness 0.1mm)/protective layer B (thickness 0.35mm) rhythmo structure.
The multilayer intermediate coat obtained is cut out vertical 30mm × horizontal 320mm.Then, between 2 transparent float glasses (vertical 25mm × horizontal 305mm × thickness 2.0mm), add multilayer intermediate coat, keep 30 minutes at 90 DEG C by vacuum laminator, carry out vacuum pressing, obtain multilayer body.In multilayer body, the middle membrane portion exposed is cut, obtain laminated glass from glass.
(embodiment 10 ~ 15)
By being used for the modification polyvinyl acetate of middle layer A and setting like that as described in Table 4 for the protection of the kind of the polyvinyl butyral resin of layer B, in addition, obtain intermediate coat and laminated glass similarly to Example 1.
(evaluation)
(1) peak maximum of the peak temperature of the Tan δ of low temperature side, the peak maximum of the Tan δ of low temperature side, the Tan δ of high temperature side
After the intermediate coat obtained is taken care of 1 month under the environment of 23 DEG C, intermediate coat is cut out the circle of diameter 8mm, use determination of viscoelasticity device (Rheometrics Co., Ltd. manufactures " ARES ") shearing method under the condition of deflection 1.0% and frequency 1Hz, carry out the temperature dispersion mensuration of dynamic viscoelastic with heat-up rate 5 DEG C/min, be determined at the peak temperature of the Tan δ that lowest temperature side occurs thus, the maximum value of the Tan δ in the peak temperature of the Tan δ of lowest temperature side appearance, and the maximum value of Tan δ in the peak temperature of the Tan δ to occur in highest temperature side.
(2) loss factor
The laminated glass obtained is taken care of one month under the environment of 20 DEG C.About the keeping laminated glass of 1 month under the environment of 20 DEG C, determinator " SA-01 " (manufacture of Rion Co., Ltd.) is used to measure loss factor by center vibratory drilling method under the condition of 20 DEG C.Loss factor (20 DEG C of loss factors) under 4 patterns (near 3150Hz) of the resonant frequency of the loss factor obtained is evaluated.
In addition, about the keeping laminated glass of 1 month under the environment of 20 DEG C, determinator " SA-01 " (manufacture of Rion Co., Ltd.) is used to measure loss factor by center vibratory drilling method under the condition of 30 DEG C.Loss factor (30 DEG C of loss factors) under 6 patterns (near 6300Hz) of the resonant frequency of the loss factor obtained is evaluated.
(3) bonding force
To polyvinyl butyral resin (b) 100 weight part with carry out mixing fully as triethylene glycol two-2-ethylhexanoate (3GO) 38 weight part of softening agent; obtain protective layer used composition, obtained the protective layer sheet material of thickness 800 μm by compression moulding.
Using the modification polyvinyl acetate that obtains in synthesis example 9 ~ 15 and triethylene glycol two-2-ethylhexanoate (3GO) 40 weight part as softening agent mixing fully, obtain middle layer composition, obtained the interlayer sheet of thickness 800 μm by compression moulding.
Protective layer sheet material and interlayer sheet are cut into width 2.5cm, at 140 DEG C, carries out hot melt after lamination glue, obtain laminated sheet.Use the laminated sheet obtained, measure bonding force (N) by 180 degree of stripping tests.In addition, in protective layer sheet material, employ 38 parts by weight of plasticizer, but also find when the softening agent of use 37.5 weight part the tendency that the size of bonding force is identical.
The details of the intermediate coat obtained and evaluation result are shown in following table 3,4.

Claims (19)

1. an intermediate film for laminated glasses, it contains modification polyvinyl acetate and softening agent, and described modification polyvinyl acetate has vinyl-acetic ester structural unit and vinyl fatty ester structural unit.
2. intermediate film for laminated glasses according to claim 1, wherein, in the described vinyl-acetic ester structural unit of described modification polyvinyl acetate and the total 100 % by mole of described vinyl fatty ester structural unit, containing described vinyl-acetic ester structural unit more than 45 % by mole, containing described vinyl fatty ester structural unit less than 55 % by mole.
3. intermediate film for laminated glasses according to claim 1 and 2, wherein, described vinyl fatty ester structural unit is the structural unit being derived from vinyl fatty ester and importing, and the carbonatoms of described vinyl fatty ester is less than 20.
4. intermediate film for laminated glasses according to claim 3, wherein, the carbonatoms of described vinyl fatty ester is more than 5 and less than 20.
5. the intermediate film for laminated glasses according to any one of Claims 1 to 4, wherein, described vinyl fatty ester structural unit is the structural unit being derived from vinyl fatty ester and importing, and described vinyl fatty ester is sad vinyl acetate, caprate, vinyl laurate, tetradecanoic acid ethene ester, vinyl palmitate, stearic acid vinyl ester, vinyl cinnamate or vinyl neodecanoate.
6. the intermediate film for laminated glasses according to any one of Claims 1 to 5, wherein, described modification polyvinyl acetate has described vinyl-acetic ester structural unit, described vinyl fatty ester structural unit and is derived from the structural unit of the monomer with carboxyl.
7. intermediate film for laminated glasses according to claim 6, wherein, described in there is carboxyl monomer be (methyl) vinylformic acid, toxilic acid, fumaric acid, β-crotonic acid, methylene-succinic acid, maleic mono-ester, fumaric monoalkylester or methylene-succinic acid monoesters.
8. the intermediate film for laminated glasses according to claim 6 or 7, wherein, the described vinyl-acetic ester structural unit of described modification polyvinyl acetate, described vinyl fatty ester structural unit and be describedly derived from the total 100 % by mole of the structural unit of the monomer with carboxyl, containing described vinyl-acetic ester structural unit more than 45 % by mole and less than 98.99 % by mole, containing described vinyl fatty ester structural unit more than 1 % by mole and less than 50 % by mole, be derived from the structural unit more than 0.01 % by mole of the monomer with carboxyl described in containing and less than 5 % by mole.
9. the intermediate film for laminated glasses according to any one of claim 1 ~ 8, wherein, described modification polyvinyl acetate, under the existence of compound with structural unit shown in following formula (X), makes described vinyl-acetic ester and described vinyl fatty ester generation copolymerization and obtains
[chemical formula 1]
In described formula (X), X1 and X2 represents the alkyl of carbonatoms 1 ~ 12, hydrogen atom or metal-salt respectively, and Y1 represents carboxylic acid group, carboxylic acid ester groups, carboxylic metallic salt or hydrogen atom, and g represents the integer of 0 ~ 3, and h represents the integer of 0 ~ 12.
10. intermediate film for laminated glasses according to claim 9, wherein, described modification polyvinyl acetate is under the existence of compound with structural unit shown in described formula (X), make described vinyl-acetic ester and described vinyl fatty ester generation copolymerization and obtain, in the total 100 % by mole of described vinyl-acetic ester and described vinyl fatty ester, described vinyl-acetic ester is more than 45 % by mole, and described vinyl fatty ester is less than 55 % by mole.
11. intermediate film for laminated glasses according to claim 9 or 10, wherein, described modification polyvinyl acetate has described vinyl-acetic ester structural unit, described vinyl fatty ester structural unit and is derived from the structural unit of the monomer with carboxyl,
Described modification polyvinyl acetate is under the existence of compound with structural unit shown in described formula (X), make described vinyl-acetic ester, described vinyl fatty ester and the described monomer with carboxyl carry out copolymerization and obtain, at described vinyl-acetic ester, described vinyl fatty ester and describedly have in the total 100 % by mole of the monomer of carboxyl, described vinyl-acetic ester is more than 45 % by mole and less than 98.99 % by mole, described vinyl fatty ester is more than 1 % by mole and less than 50 % by mole, the described monomer with carboxyl is more than 0.01 % by mole and less than 5 % by mole.
12. intermediate film for laminated glasses according to any one of claim 1 ~ 11, wherein, in the described vinyl-acetic ester structural unit of described modification polyvinyl acetate and the total 100 % by mole of described vinyl fatty ester structural unit, containing described vinyl-acetic ester structural unit more than 50 % by mole, containing described vinyl fatty ester structural unit less than 50 % by mole.
13. intermediate film for laminated glasses according to any one of claim 1 ~ 12, wherein, the polymerization degree of described modification polyvinyl acetate is more than 1000 and less than 9000.
14. intermediate film for laminated glasses according to any one of claim 1 ~ 13, it has the Rotating fields only possessing the first layer or the two-layer above rhythmo structure possessing the first layer and other layer, wherein, described the first layer contains described modification polyvinyl acetate and described softening agent.
15. intermediate film for laminated glasses according to any one of claim 1 ~ 14, it second layer of first surface possessing the first layer and be stacked on described the first layer, described the first layer contains described modification polyvinyl acetate and described softening agent.
16. intermediate film for laminated glasses according to claim 15, wherein, the described second layer contains polyvinyl acetal resin,
The degree of acetylation of polyvinyl acetal resin described in the described second layer is less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.
17. intermediate film for laminated glasses according to claim 15 or 16, it possesses third layer further, and it is stacked on the second surface contrary with described first surface of described the first layer.
18. intermediate film for laminated glasses according to claim 17; wherein; described third layer contains polyvinyl acetal resin, and the degree of acetylation of polyvinyl acetal resin described in described third layer is less than 15 % by mole, and the containing ratio of hydroxyl is more than 20 % by mole.
19. 1 kinds of laminated glass, it possesses the first laminated glass component parts, the second laminated glass component parts and the intermediate film for laminated glasses according to any one of claim 1 ~ 18, and described intermediate film for laminated glasses is clipped between first, second laminated glass component parts described.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108883983A (en) * 2016-03-28 2018-11-23 株式会社可乐丽 Intermediate film for laminated glasses
WO2019096024A1 (en) * 2017-11-20 2019-05-23 Chang Chun Petrochemical Co., Ltd. Multilayer film, interlayer film comprising the multilayer film and laminated glass and sound-insulating glass laminate comprising the interlayer film

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2803648B1 (en) * 2012-01-13 2018-08-22 Sekisui Chemical Co., Ltd. Intermediate film for laminated glass, and laminated glass
US11673979B2 (en) 2015-08-12 2023-06-13 Denki Kagaku Kogyo Kabushiki Kaisha Binder for glass paper
JP6885404B2 (en) * 2016-08-05 2021-06-16 Ａｇｃ株式会社 Laminated glass
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WO2018212331A1 (en) 2017-05-19 2018-11-22 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446767A (en) * 1963-09-18 1969-05-27 Permutit Co Ltd Terpolymer of vinyl acetate-vinyl tertiary acid esters and acrylate,maleate or fumarate ester
US3519587A (en) * 1966-10-31 1970-07-07 Wacker Chemie Gmbh Pressure sensitive adhesives of vinyl acetate/vinyl laurate copolymers
US4382996A (en) * 1979-05-31 1983-05-10 Sekisui Kagaku Kogyo Kabushiki Kaisha Laminated safety glass
US7078455B2 (en) * 2001-03-15 2006-07-18 Celanese Emulsions Gmbh Aqueous plastic material dispersions method for producing the same and use thereof
CN101426746A (en) * 2006-04-25 2009-05-06 积水化学工业株式会社 Intermediate film for laminated glass and laminated glass
CN101824290A (en) * 2008-12-29 2010-09-08 赛拉尼斯乳胶有限公司 Vinyl acetate/2 ethyl hexanoic acid vinyl ester copolymers adhesive resin

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3952135A (en) * 1972-01-18 1976-04-20 Imperial Chemical Industries Limited Laminated glass windows for vehicles
JPH0639339B2 (en) * 1985-10-28 1994-05-25 積水化学工業株式会社 Interlayer film composition for safety laminated glass
JPH0532434A (en) * 1991-08-01 1993-02-09 Sekisui Chem Co Ltd Production of intermediate membrane for light-scattering laminated glass and production of light-scattering laminated glass
JPH11255827A (en) 1998-03-12 1999-09-21 Sekisui Chem Co Ltd Polyvinyl acetal resin and laminate glass interlayer using same
JP2007070200A (en) 2005-09-09 2007-03-22 Asahi Glass Co Ltd Laminated glass
DE102007044788A1 (en) * 2007-09-19 2009-04-02 Wacker Chemie Ag Preparation of vinyl acetate-vinyl ester copolymers with low content of high-boiling vinyl esters
JP2009161584A (en) * 2007-12-28 2009-07-23 Denki Kagaku Kogyo Kk Polyvinyl acetal composition containing polyvinyl acetate, polyvinyl acetal sheet comprising the polyvinyl acetal composition, and interlayer film for laminated glass comprising the polyvinyl acetal composition
EP2153989B1 (en) * 2008-08-01 2021-09-29 Kuraray Europe GmbH Multi-layer films from polyvinylacetal containing plactisizer with sound absorbing characteristics
EP2660216B1 (en) * 2010-12-28 2021-04-07 Sekisui Chemical Co., Ltd. Interlayer for laminated glass and laminated glass

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446767A (en) * 1963-09-18 1969-05-27 Permutit Co Ltd Terpolymer of vinyl acetate-vinyl tertiary acid esters and acrylate,maleate or fumarate ester
US3519587A (en) * 1966-10-31 1970-07-07 Wacker Chemie Gmbh Pressure sensitive adhesives of vinyl acetate/vinyl laurate copolymers
US4382996A (en) * 1979-05-31 1983-05-10 Sekisui Kagaku Kogyo Kabushiki Kaisha Laminated safety glass
US7078455B2 (en) * 2001-03-15 2006-07-18 Celanese Emulsions Gmbh Aqueous plastic material dispersions method for producing the same and use thereof
CN101426746A (en) * 2006-04-25 2009-05-06 积水化学工业株式会社 Intermediate film for laminated glass and laminated glass
CN101824290A (en) * 2008-12-29 2010-09-08 赛拉尼斯乳胶有限公司 Vinyl acetate/2 ethyl hexanoic acid vinyl ester copolymers adhesive resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108883983A (en) * 2016-03-28 2018-11-23 株式会社可乐丽 Intermediate film for laminated glasses
US11325354B2 (en) 2016-03-28 2022-05-10 Kuraray Co., Ltd. Interlayer film for laminated glass
WO2019096024A1 (en) * 2017-11-20 2019-05-23 Chang Chun Petrochemical Co., Ltd. Multilayer film, interlayer film comprising the multilayer film and laminated glass and sound-insulating glass laminate comprising the interlayer film
CN110536797A (en) * 2017-11-20 2019-12-03 长春石油化学股份有限公司 Multilayer film, the intermediate coat comprising the multilayer film and the laminated glass comprising the intermediate coat and sound control glass laminate

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